Flux pinning of cuprate superconductors with nanoparticles

ABSTRACT

The present invention provides a method of making a high temperature superconductor having a doped, nanoparticulate pinning structure. The method includes providing a nanoparticulate pinning material, providing a cuprate material, doping the nanoparticulate pinning material with a dopant to form a doped nanoparticulate material, depositing a layer of the cuprate material on a substrate, and depositing a layer of the doped nanoparticulate material on the layer of cuprate material. The invention also provides a high temperature superconductor (HTS) having a doped, nanoparticulate pinning structure including a plurality of layers of a cuprate material and a plurality of layers of a doped nanoparticulate pinning material. At least one layer of the doped nanoparticulate pinning material is stacked between two layers of the cuprate material.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a division of U.S. patent application Ser. No. 12/023,973, filed Jan. 31, 2008, titled “Flux Pinning of Cuprate Superconductors with Nanoparticles,” now U.S. Pat. No. 8,383,552. It claims priority from that application and from U.S. Provisional Patent Application 60/887,478, filed Jan. 31, 2007, titled “A New Architecture to Incorporate Relevant Flux Pinning Materials into High Temperature Superconductors.” The present application is related to, but does not claim priority from, U.S. patent application Ser. No. 11/543,286, filed Oct. 3, 2006, now U.S. Pat. No. 7,871,663, titled “Minute Doping for YBCO Flux Pinning.” patent application Ser. Nos. 12/023,973, 60/887,478 and 11/543,286 are incorporated by reference into this description.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.

FIELD OF THE INVENTION

The present invention relates generally to high temperature superconductors and more specifically to a method of imparting magnetic flux pinning within a high temperature superconductor to improve current transport by introducing dopants and/or nanoparticles into the superconducting material.

BACKGROUND OF THE INVENTION

High Temperature Superconductors (HTS) are type II superconductors that react in a known manner when exposed to applied magnetic fields. When an HTS is exposed to a magnetic field >Hcl at approximately 20 mT, the magnetic field enters the superconductor as a self-interacting lattice of quantized line vortices or fluxons. Each fluxon is a tube of radius London penetration depth λ(T) with superconducting current circulating around a non-superconducting core of radius on the order of the coherence length ζ(T). The magnetic field trapped in each fluxon is quantized with a value 2×10⁻¹⁵ Wb.

To carry a stable current, the fluxon lattice in the superconductor must be prevented from moving by pinning each fluxon in an area that contains a non-superconducting material or defect. The size of pinning defects should be on the order of the coherence length, approximately 1-2 nm at 4.2K and 2-4 nm at 77K. The introduction of any type of intrinsic or extrinsic defect can act as effective pinning center. Introduction of extrinsic defects provide a straightforward method to control flux pinning, without disturbing the superconductor.

Extrinsic defects have been added by a variety of processes which typically fall into two categories: irradiation or bombarding the HTS films with energetic particles which displaces material leaving tracks, or by incorporating small inclusions of alternate material into the films. Irradiation is considered too expensive to be practical.

The desirability of providing efficient high temperature superconductors for operation at 20° K and higher is well known. Indeed, there has been an enormous amount of experimental activity in these so called high temperature superconductors since research in the mid 1980s first demonstrated dramatic gains in raising the maximum critical transition temperatures from the 20° K range to the 90° K range.

In general, superconductors and superconducting material exhibit zero resistance when operating at temperatures below their maximum critical transition temperature. This quality of operating at zero resistance facilitates the construction and operation of highly efficient devices such as superconducting magnets, magnetic levitators, propulsion motors and magnetohydronamics, power generators, particle accelerators, microwave and infrared detectors, etc.

High temperature superconducting (HTS) generators and magnets are significantly lighter and more compact than their conventional counterparts. The development of these devices is essential to military applications requiring compact, lightweight, high power sources or compact high field magnets, especially ground mobile, airborne and naval applications. The high temperature superconducting coated conductor can be used to make the coil windings in HTS generators as well as the HTS magnet windings. As such, long lengths of the YBCO coated conductor with high current transport in a magnetic field are necessary for effective use in these applications.

Given the important role high temperature superconductors will play in future technology, several attempts have been made to improve high temperature superconductors. For example, Calcium (Ca) doping at Y site in Y123 films has been studied extensively, as Ca is expected to increase the population of holes in Y123 by replacing Y⁺³ with Ca⁺² hence improving superconductor coupling between the grains (intergranularly). Scientists have reported a 2 to 6 fold improvement of critical current density (J_(c)) between large-angle grains (intergranular J_(c)) for annealed Y123/Ca-Y123/Y123 multi-layer films at 77K and lower temperatures, however only for very large angle grain boundaries 24° [001] ab in-plane misorientation. Other scientists have reported that Ca doping increased the intergranular critical current density in spite of a lower critical transition temperature (T_(c)) in higher concentrations of Ca doped Y123 films; however such increases were only measured well below T_(c) at about 60K or less.

In U.S. Pat. No. 6,830,776 (along with other references), Barnes et al. demonstrated that Y123/Y211 nanoparticulates/Y123 multi-layers exhibit highest magnetization J_(c) due to uniform distribution of nano-ordered pinning centers.

There is a further need for low-cost methods for incorporating inclusions or defects into HTS. The present invention addresses this need by providing 1) minute quantities of rare earth elements or other deleterious elements in YBCO thin films and 2) providing a combination effect of Ca doping as well as 211 pinning in Y123 materials to increase the critical current carrying capability across grain boundaries as well as in high magnetic fields.

SUMMARY OF THE INVENTION

In one embodiment, the present invention incorporates the substitution or addition of minute quantities of rare earth elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) or other deleterious elements (Sc, etc.) in YBCO thin films to achieve the appropriate defect densities for enhanced flux pinning. Advantageously, the method of the present invention enables enhanced flux pinning of the material while not significantly increasing the cost of the HTS material or processing parameters. The minute doping approach of the present invention can be used in all HTS deposition methods such as MOCVD, MOD, PLD, sol-gel, sputtering electrolytic deposition, etc., since it is not process dependent.

In another embodiment, the invention provides a new architecture to incorporate relevant flux pinning materials into high temperature superconductors for achieving high critical currents in magnetic fields. This embodiment combines: 1) the advantages of Ca doping to improve intergranular supercurrents and 2) the advantages of further doping nanoparticulate inclusions with Ca for magnetic flux pinning to improve the intragranular supercurrents.

More specifically, this embodiment of the invention addresses the improvement of the supercurrent carrying capabilities of epitaxial or bi-crystalline or polycrystalline high temperature superconductors, especially RBa₂Cu₃O_(7-x) (RBCO) where R=(Y, rare earths) superconducting coated conductors. This is accomplished by providing a nanoparticulate pinning structure with appropriate predetermined nanoscale insulating pinning materials throughout the superconducting film and by doping appropriate amount of Ca into the insulating pinning material. Using Ca-doping, the space charge layers at the grain boundaries can be reduced and thereby the current transport properties of the superconducting film can be significantly improved.

Also, due to the pinning nature of the insulating material, the influence of magnetic fields on the critical densities is significantly reduced, which further enhances the overall supercurrent carrying capabilities. These things are accomplished while keeping the critical temperature and transport properties of the films at reasonably elevated values when compared with pure RBCO films. An exemplary method of the invention combines into a single step the advantages of Ca-doping to improve intergranular supercurrents with the advantages of nanoparticulate inclusions for magnetic flux pinning to improve the intragranular supercurrents. By this method, these simultaneous advantages can be achieved, however without decreasing the critical transition temperature of the Y123 superconducting layer which typically occurs with Ca addition.

For demonstration, Y_(2-x)Ca_(x)BaCuO₅ (where x is approximately 0 to 10% of Y molar fraction) is the pinning material. However, the process can also use Ca-doping of any material to be used for the particulate inclusions in the superconductor. The nanoparticulate dispersion in the HTS material was demonstrated using pulsed laser deposition; however, the process could be applied to other HTS materials and using other thin film deposition or coating techniques such as Molecular Beam Epitaxy, sputtering, metal oxide deposition, e-beam evaporation, sol-gel, Metal oxide chemical vapor deposition etc. to insert the nanoparticulates.

In accordance with one aspect of the invention, there is provided a method of making a high temperature superconductor having a doped, nanoparticulate pinning structure. The method includes providing a nanoparticulate pinning material, providing a cuprate material, doping the nanoparticulate pinning material with a dopant to a form doped nanoparticulate material, depositing a layer of the cuprate material on a substrate, and depositing a layer of the doped nanoparticulate material on the layer of cuprate material.

The nanoparticulate pinning material may be an oxide. For example, the pinning material may be Y_(2-x)BaCuO₅ (Y211) or R_(2-x)BaCuO₅ (R211), where R is a rare earth element. The cuprate material is a superconductor material. For example, the cuprate material may be YBa₂Cu₃O_(7-x)(Y123) or RBa₂Cu₃O_(7-x) (R123), wherein R is a rare earth element.

The steps of depositing may include depositing alternating stacked layers of the cuprate material and the doped nanoparticulate material on the substrate. The alternating stacked layers may total about 40 to 70 layers. At least one of the depositing steps may be performed by pulsed laser deposition, Metal-Organic Chemical Vapor Deposition (MOCVD), Metal-Organic Deposition (MOD), sol-gel, sputtering electrolytic deposition, and other suitable techniques.

In accordance with another aspect of the invention, there is provided a high temperature superconductor (HTS) having a doped, nanoparticulate pinning structure. The HTS includes a plurality of layers of a cuprate material and a plurality of layers of a doped nanoparticulate pinning material. At least one layer of the doped nanoparticulate pinning material is stacked between two layers of the cuprate material.

The cuprate material may be YBa₂Cu₃O_(7-x) (Y123) or RBa₂Cu₃O_(7-x) (R123), wherein R is a rare earth element. The doped nanoparticulate pinning material may be a doped oxide, such as Y_(2-x)D_(x)BaCuO₅ (doped Y211) where D is a dopant or such as R_(2-x)D_(x)BaCuO₅ (doped R211), where R is a rare earth element and D is a dopant. The dopant may be a hole donor element. For example, the dopant may be Calcium, Cobalt, or Magnesium.

BRIEF DESCRIPTION OF THE DRAWING

The accompanying drawing incorporated in and forming a part of the specification, illustrates several aspects of the present invention and together with the description serves to explain the principles of the invention. In the drawing:

FIG. 1 is a graph illustrating the magnetic J_(c) values of Y_(1-x)M_(x)Ba₂Cu₃O_(7-z) films, where M stands for deleterious elements (i.e. rare earth elements, Sc, etc.) compared to a reference Y123 film made using the same deposition conditions at 77K and H//c-axis.

FIG. 2 is a graph illustrating the magnetic J_(c) values of Y_(1-x)MBa₂Cu₃O_(7-z) films compared to a reference Y123 film made using the same deposition conditions at 65K and H//c-axis.

FIG. 3 is a graph illustrating J_(ct) across [010]c-axis tilt grain boundaries with misorientation angle of 6° versus deposition temperature for Ca-doped 211 with Y123 and Y211 with YBCO compared to YBCO. For (M/YBCO)_(N) multilayer films the M=Ca-doped 211 or Y211 layer thickness was 0.4-0.7 nm thickness, the YBCO layer thickness was 5-11 nm, and the number of N bilayers was from 20-28, and the bicrystal substrate was single-crystal SirTiO₃.

FIG. 4 is a graph illustrating magnetic J_(c) values (J_(cm)) versus H_(appl) measured on LaAlO₃ or SrTiO₃ single crystal substrates for Ca-doped 211, Y211, and YBCO at 40K, 65K and 77K; For (M/YBCO)_(N) multilayer films the M=Ca-doped 211 or Y211 layer thickness was 0.4-0.5 nm thickness, the YBCO layer thickness was 8-10 nm, and the number of N bilayers was 28.

DETAILED DESCRIPTION OF THE INVENTION

The following section describes the substitution or addition of minute quantities of rare earth elements or other deleterious elements in YBCO thin films to achieve the appropriate defect densities for enhanced flux pinning. Additionally, this section describes improvements to high temperature superconductors concerning the incorporation of nanoparticles into superconductor material for magnetic flux pinning with nanoparticulate material that is doped.

Firstly, the present invention relates, in part, to a method of imparting magnetic flux pinning within a high temperature superconductor to improve current transport by introducing minute quantities of dopants into the material. According to the method of the present invention, substitution of small quantities (x≦0.02) of rare earth elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) or other deleterious elements (Sc, etc.) for Y in Y123 thin films has been demonstrated to achieve the appropriate defect densities for enhanced flux pinning. As used herein, “deleterious element” is intended to refer to a material that in large quantities would degrade the performance of the superconductor in an undesirable fashion. The method of the present invention enables enhanced flux pinning of the material while not significantly increasing the manufacturing cost of the HTS material. Additionally, the minute doping approach of the present invention can be used in all HTS deposition methods such as Metal-Organic Chemical Vapor Deposition (MOCVD), Metal-Organic Deposition (MOD), Pulsed Laser Deposition (PLD), sol-gel, sputtering electrolytic deposition, etc., since it is not process dependent.

Coated conductor technology for biaxially aligned YBa₂Cu₃0_(7-z). (Y123) on buffered metallic substrates with J_(c)>1 MA/cm² offers great promise as a second generation, high temperature superconducting wire for use in generators and motors. Y123 has many useful properties at 77K such as high critical current densities (J_(c)) and good flux pinning in applied magnetic fields, which is critical in most applications. However, when magnetic fields are applied parallel to the c-axis, J_(c) will typically decrease by a factor of 10 to 100 within the range of 1 T<B_(appl)<5 T. Accordingly, further improvement of J_(c) is desirable, especially for c-axis orientation of the applied field, to allow further reduction in system weight and size. In most applications, the value J_(c)(H) places an upper limit on the magnetic field that can be produced/applied for a given coil design.

Recently, REBa₂Cu₃O_(7-z) (RE123) (where RE stands for rare earth elements) superconductors have been considered for use in applications of thin film coated conductors because of their desirable high critical transition temperatures (T_(c)) (˜92 K), and high critical current density (J_(c)) at 77 K in applied magnetic fields. According to the method of the present invention, the partial substitution of rare earth elements or other deleterious elements (herein represented as M) in the (Y_(1-x)M_(x))Ba₂Cu₃0_(7-z), (x≦0.02), as dopants, has been demonstrated to enhance flux pinning. As an example, Tb, Ce and Pr are divalent, having both +3 and +4 valance states and can act as pinning sites by localized lattice distortion or other potential mechanism. Even if a rare earth can readily form the proper REBCO superconducting phase, as in the case of Nd and La, they can be poor dopants in YBCO by substituting undesirably into the Ba site, degrading the superconductor's performance. However, in small quantities, these Ba substitutions can also act as a potential pinning mechanism. In addition, using small quantities of dopants allows the same processing conditions to be used for making high quality YBCO.

An example of the method of the present invention using terbium as a dopant follows. Terbium does not degrade the T_(c) of Y123 and the divalent nature of terbium (+3 and +4 valence states) can allow for Tb⁴⁺ to act as pinning sites by alternate chemical bonding, localized lattice distortion, or other methods. The crystal ionic radii of Tb⁽⁺³⁾ is 1.04 Å which is quite close to the ionic radii of Y⁽⁺³⁾ of 1.02 Å. Because Tb123 is normally processed as a non-superconducting phase, the substitution of Tb123 for Y123 into a bulk or thin film superconductor has the potential to create localized regions of size on the order of one unit cell or larger of either reduced T_(c) regions or potential site defects. Such regions can provide the non-superconducting pinning centers with particle densities approaching 1.5-3×10¹¹ cm⁻² which are necessary to pin magnetic fields of ˜3-6 T.

According to the method of the present invention, precursor materials (i.e. laser ablation targets in the case of pulsed laser deposition) were manufactured in-house by the following procedure: Y_(0.9)Tb_(0.1)Ba₂Cu₃O_(7-z) powder was prepared from Y₂0₃, BaCO₃, CuO, and Tb₄O₇ powder (all nominally 99.99+% pure). The powders were dried, mixed, and then calcined at 850° C. and 880° C. This powder was then used to make two targets of compositions Y_(0.9)Tb_(0.1)Ba₂Cu₃O_(7-z) and Y_(0.99)Tb_(0.01)Ba₂Cu₃O_(7-z) with the second composition consisting of 10 mol % Y_(0.9)Tb_(0.1)Ba₂Cu₃O_(7-z) and 90 mol % Y123 powder. The targets were then fully reacted at 940° C. and 920° C. respectively for 50 hours. The Y_(0.9)Tb_(0.1)Ba₂Cu₃O_(7-z) target was found to be 84.8% dense and the Y_(0.99)Tb_(0.01)Ba₂Cu₃O_(7-z) target was found to be 88.7% dense. The estimated purity of the targets was 99.99+% pure.

Next, multiple compositions of (Y,Tb)123 films were deposited by pulsed laser deposition, using parameters and conditions optimized previously for Y123. The depositions were performed on strontium titanate (STO) and lanthanum aluminate (LAO) substrates with the overall time for film growth being about 20 minutes. Depositions were performed using a Lambda Physik, LFX 300 KrF excimer laser (λ=248 nm). The laser pulse rate was 4 Hz and the laser fluence was ˜3.2 J/cm². The target-to-substrate distance was kept at 6 cm for all of the depositions. The oxygen pressure during the deposition was 300 mTorr for both of the Y,Tb-123 targets, as measured with capacitance manometer and convectron gauges within <10% variation. Oxygen gas (>99.997% purity) flowed into the chamber during growth and the oxygen pressure in the chamber was kept constant using a downstream throttle-valve control on the pumping line. The laser beam was scanned across the targets to improve thickness uniformity of the film. The LaAlO₃ (100) and SrTiO₃ (100) single crystal substrates were ultrasonically cleaned for 2 minutes, using first acetone followed by isopropyl alcohol. Crystalline substrates were provided by the manufacturer epitaxially polished on both sides of the LaAlO₃ and on one side for SrTiO₃, and were attached to the heater using a thin layer of colloidal Ag paint. LAO and STO substrate sizes were ˜3.2×3.2 mm² for magnetic Jc measurements.

The background pressure in the chamber was reduced to <1.4×10⁴ torr prior to deposition. Samples were heated from room temperature to the deposition temperature of 775° C. at ˜1270° C./h. After deposition, the vacuum pumps and O₂ pressure control were shut off and the films were cooled radiantly from 775° C. to 500° C. while increasing the O₂ pressure to 1 atm. The temperature was then held at 500° C. for 30 minutes. The films were then cooled to room temperature. The (Y,Tb)123 layer thickness was estimated by comparing previous deposition runs in the chamber using the same deposition parameters.

Magnetic J_(c) measurements were made with a Quantum Design Model 6000 Physical Property Measurement System (PPMS) with a vibrating sample magnetometer (VSM) attachment in fields of 0 to 9 T, and a ramp rate 0.01T/s. The J_(c) of the square samples was estimated using a simplified Bean model with J_(c)=30 ΔM/da³ where ΔM is in emu, film thickness d and lateral dimension a are in cm and J is in A/cm². Samples were subsequently acid-etched at the corners of the samples for thickness measurements. A P-15 Tencor profilometer was used to measure the thickness of the (Y,Tb)123 films. Care was used to measure in twin-free areas of the LaAlO₃ substrates, which were observed visually at high magnification. The film thickness and dimensions of each sample were measured multiple times to reduce errors in determination of the superconducting volume and a to <5%.

The results of J_(c) measurements that were performed on several samples made using this invention are shown in FIGS. 1 and 2. FIG. 1 shows the magnetic J_(c) values of the Y_(1-x)M_(x)Ba₂Cu₃O_(7-z) films at 77K compared to a reference 123 film made using the same deposition conditions. At elevated field, the J_(c) values of the samples made using this invention exceeded the standard Y123 values by more than 2000% (6 T, 77K, H//c-axis, M=Tb, x=0.01). FIG. 2 shows the magnetic J_(c) values of the Y_(1-x)M_(x)Ba₂Cu₃O_(7-z) films at 65K compared to a reference 123 film made using the same deposition conditions. At elevated field, the J_(c) values of the samples made using this invention exceeded the standard Y123 values by more than 200% (8.9 T, 77K, H//c-axis, M=Tb, x=0.01).

Thus, the minute doping method of the present invention has been demonstrated to provide enhanced flux pinning within HTS materials. Additionally, while the invention has been described in terms of pulsed laser deposition techniques, it is not considered so limited. The minute doping approach of the present invention can be used in all HTS deposition methods such as MOCVD, MOD, PLD, sol-gel, sputtering electrolytic deposition, etc., since it is not process dependent.

The remaining portion of this section describes further improvements to high temperature superconductors. That is, doped nanoparticles are incorporated into superconductor material for magnetic flux pinning and grain boundary enhancements. For example, an oxide is doped with a dopant and is combined with a cuprate superconductor material to improve intergranular and intragranular supercurrents without significantly degrading the critical temperature T_(c) and critical currents. The doped oxide is deposited on or in the cuprate material as nanoparticles. The concentration of dopant additions into the nanoparticles may be in the range of 1%-15% by molar fraction substitution. In an exemplary embodiment, the concentration is 10% by molar fraction substitution. The concentration of nanoparticle additions into YBCO are in the range of 1%-20% by volume fraction, or alternatively the spacing of nanoparticles may be in the range of 3-30 nm. The oxide may be any oxide known by one skilled in the art to be used with cuprate superconductor material. Examples of oxides are Y_(2-x)BaCuO₅ (Y211) and R_(2-x)BaCuO₅ (R21). Examples of cuprate material that may be used in this invention include YBa₂Cu₃O_(7-x) (Y123) or RBa₂Cu₃O_(7-x) (R123) where R is a rare earth material as previously described. The dopant may be any hole donor element, for example, Calcium, Cobalt, or Magnesium.

The inventive process entailed ablating YBa₂Cu₃O₇(Y123) and Y_(2-x)Ca_(x)BaCuO₅ (Ca-doped Y211) targets using the output of a KrF (248 nm) excimer laser and doing this with conditions ranging from 200-500 mTorr of O₂ pressure and 750°-850° C. substrate temperature. Ca-doped Y211 (Y_(2-x)Ca_(x)BaCuO₅) layers were deposited with a thickness in the range of approximately 0.4-0.7 nm, for example 0.6 nm thick. These layers were alternated with layers of YBa₂Cu₃O_(7-x) with a thickness in the range of 5-10 nm, for example 9 nm thick. Approximately 40-70 layers of 211 alternated with 123 were deposited, for total film thickness of about 0.3 micron. Following deposition, the film was cooled and annealed at 500° C. in 1 atm of O₂. Films were also deposited onto SrTiO₃ bicrystals with grain boundaries misorientations of 6°, 12°, 24° and 36°, to measure the effect of Ca-doped 211 additions on grain boundary transports.

The pinning properties were measured in magnetic fields up to 9 T using a Vibrating Sample Magnetometer (VSM). The electrical transport measurements were done at 77K in self-field. Microstructure was investigated using Cross sectional Transmission Electron Microscopy. The primary architecture consisted of alternating layers of R123 with nano-layered Ca doped R211 materials. Nano layered materials can be either Ca-doped R211 or other Ca-doped oxides that provide effective pinning, e.g. Ba_(x)Ca_(1-x)ZrO₃. A bi-axially textured substrate with buffer layers (either processed using RABITS method or IBAD method) of any chemically compatible materials with RBCO comp can be coated with the above multi-layer architecture in order to achieve better electrical transport properties in self field or high magnetic field.

During testing of the invention, the deposition was performed using PLD conditions optimized to provide maximum critical transition temperature (T_(c)) and critical current density (J_(c)) in the YBCO-123 film layer. The non-superconducting material was chosen to be Y_(2-x)Ca_(x)BaCuO₅ (Ca-doped 211) with x=0.05 to 0.1. Nanoparticles of almost the same size and areal number density were achieved with Ca-doped 211 compared to Y211, as observed by cross-sectional TEM. The flux pinning properties were measured. The J_(c) for a multilayer YBCO sample with Ca-doped 211 interlayers deposited onto single crystal substrates was observed to increase by 2-3 times for applied magnetic fields up to 2 Tesla at 65K-77K compared to similar thickness YBCO-only films without 211 interlayers, and a small but measurable increase compared to YBCO films with 211 (instead of Ca-doped 211) interlayers. This is a single step process (i.e. doping 211 with Ca and applying the Ca-doped 211 as nanoparticles). This single step process significantly improves HTS and results in considerable cost savings when applied to long length conductors. Importantly, this method of Ca-addition did not reduce the superconducting transition temperature in multiple tests, which is typically observed with other methods of Ca-doping directly onto the Y123 layer. As a result, a positive increase of J, across STO bicrystal grain boundaries particularly at 77K is a possibility with this sort of Ca-doping method, which does not degrade the flux pinning properties.

In the drawings, FIG. 3 shows that Ca-doped 211 with YBCO has the greatest J_(ct) across [010] c-axis tilted grain boundaries of 6° when compared to Y211 with YBCO and compared to YBCO. Similar increases of J_(c) of 2× were achieved for GB angles from 6°-12°, and large increases of J_(c) of 8×-30× were achieved for very large angle GB's of 24°-36°. This demonstrates that Ca-doped 211 provides strong increase of J_(c) across grain boundaries of different orientation angles and structures. FIG. 4 shows that Ca-doped 211 with YBCO has the greatest J_(cm) in magnetic fields up to 9 Tesla at 40K, 65K and 77K measured on single-crystal substrates with average grain boundary angles <1°. This demonstrates that Ca-doped 211 also does not degrade the magnetic field dependence (flux pinning) of the grains themselves, but further improves it. FIGS. 3 and 4 indicate that Ca-doped 211 increases J_(c) both inside the grains (intragranular) with flux pinning enhancements and across high-angle grain boundaries (intergranular) simultaneously. The physical mechanisms to improve J_(c) across grain boundaries and in magnetic fields are not necessarily related, so this achievement is notable and important to enable both of these processes to be improved simultaneously in YBCO wire manufacturing.

The preceding embodiment of HTS having Ca-doped 211 with Y123 was created using pulsed laser deposition techniques. However, the doping and nanoparticle approach of the invention can be used in all HTS deposition methods such as MOCVD, MOD, PLD, sol-gel, sputtering electrolytic deposition, and other techniques known to one with ordinary skill in the art.

It is further contemplated that preceding processes and resulting superconductors may be modified to form yet another embodiment of the present invention. That is, Y211 nanoparticles may be deposited onto or within YBCO. The manufacturing methods previously described may be applied by one with skill in the art to form Y211 nanoparticles with YBCO. As seen in FIGS. 3 and 4, Y211/YBCO was tested and exhibits strong superconducting properties, both intragranularly and intergranularly. This demonstrates for the first time ever that an ionic dopant other than Ca can strongly enhance YBCO grain boundary properties at 77K. This new invention indirectly suggests physical mechanisms rather than electronic dopants can be suitable to provide grain boundary healing. For example, healing occurs by choosing or finding the right dopant atom with proper ionic size to fill the grain boundary porosities and dislocations. High temperature deposition at 825° C. was also observed to be critically important to enable this effect, as shown in FIG. 3. At this higher temperature of 825° C., YBCO has been observed with transmission electron microscopy (TEM) to form more perfect lattice structures, which suggests the higher temperature provides a softening effect allowing the film structures to grow more evenly and even out stresses. These stresses and film relaxations may be critical mechanisms to healing and covering the grain boundary, and allows the dopant additions to have the strong effects. Previously, dopants including Pt, Ag, Co, Ni, Pt, and Fe were tested by scientists without improvement, but rather with further degradation of grain boundary J_(c)s.

The foregoing description of the illustrated embodiment has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiment described was chosen to provide an illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled. 

We claim:
 1. A method for making a high temperature superconductor having a doped, nanoparticulate pinning structure, comprising: (a) providing a nanoparticulate pinning material, wherein the nanoparticulate pinning material is an oxide and wherein the oxide is Y_(2-x)BaCuO₅ (Y211); (b) providing a cuprate material; (c) doping the nanoparticulate pinning material with a dopant to form a doped nanoparticulate material; (d) depositing a layer of the cuprate material on a substrate; and, (e) depositing a layer of the doped nanoparticulate material on the layer of cuprate material.
 2. A method for making a high temperature superconductor having a doped, nanoparticulate pinning structure, comprising: (a) providing a nanoparticulate pinning material, wherein the nanoparticulate pinning material is an oxide and wherein the oxide is R_(2-x)BaCuO₅ (R211), where R is a rare earth element; (b) providing a cuprate material; (c) doping the nanoparticulate pinning material with a dopant to form a doped nanoparticulate material; (d) depositing a layer of the cuprate material on a substrate; and, (e) depositing a layer of the doped nanoparticulate material on the layer of cuprate material. 